Diurethanes

ABSTRACT

New and valuable diurethanes having a good herbicidal action, herbicides containing these compounds, and a process for controlling the growth of unwanted plants with these compounds.

The present invention relates to new and valuable diurethanes having a herbicidal action, herbicides containing these compounds, and a process for controlling the growth of unwanted plants with these compounds.

It is known to use 2-sec-butyl-4,6-dinitrophenol (U.S. Pat. No. 2,192,197), ethyl-N-(3-N'-phenylcarbamoyloxy)-phenyl)-carbamate and methyl-N-(3-(N'-(3'-methylphenylcarbamoyloxy)-phenyl)-carbamate (German Printed Application DAS 1,567,151), 3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide (German Printed Application DAS No. 1,542,836), and 1-phenyl-4-amino-5-chloropyridazone-(6) (German No. 1,105,232) as herbicides. These compounds are established herbicides with special areas of application.

We have now found that new diurethanes of the formula ##STR1## where R¹ and R² are identical or different and each denotes hydrogen, alkyl (e.g., methyl, ethyl, isopropyl), alkoxyalkyl (e.g., methoxymethyl, 2-methoxyethyl), haloalkyl (e.g., chloromethyl), unsubstituted benzyl, or benzyl substituted by alkyl or halogen, R³ and R⁴ are identical or different and each denotes unsubstituted alkyl, alkyl substituted by halogen, alkoxy or substituted or unsubstituted aryl (e.g., methyl, ethyl, 2-chloroethyl, 2-methoxyethyl, benzyl, isopropyl, n-propyl, 4-chlorobenzyl, n-butyl, sec.-butyl, tert.-butyl, isobutyl, 2,4-dichlorobenzyl, 2-ethylhexyl, n-decyl), unsubstituted or halogen-substituted alkenyl (e.g., allyl, 2-chloropropen-(1)-yl-(3), buten-(1)-yl-(3)), unsubstituted or halogen- or alkoxy-substituted alkynyl (e.g., propargyl, butyn-(1)-yl-(3), 1-chlorobutyn-(2)-yl-(4), unsubstituted or alkyl-substituted cycloalkyl (e.g. cyclopentyl, cyclohexyl, 3-methylcyclohexyl, 2,6-dimethylcyclohexyl, cycloheptyl, 4-tert.-butylcyclohexyl, cyclooctyl, cyclododecyl, 3,5-dimethylcyclohexyl), bicycloalkyl (e.g., norbornyl), tricycloalkyl (e.g., tricyclo[4,3,1²,5 0¹,6 ]-decyl), phenyl with fused ring system (e.g., naphthyl, benzofuranyl, indyl), phenyl, mono- or polysubstituted phenyl with the substituents alkyl, haloalkyl, alkoxyalkyl, cycloalkyl, halogen, alkoxy, haloalkoxy, alkoxycarbonylalkoxy, nitro, amino, aryl, aryloxy, thiocyanate, cyano, (e.g., phenyl, 4-fluorophenyl, 2-methoxyphenyl, 3-methylphenyl, 2-fluorophenyl, 3-methyl-5-isopropylphenyl, 3-ethylphenyl, 3-chlorophenyl, 2,4,6-trimethylphenyl, 3-fluorophenyl, 3-chloro-4-fluorophenyl, 3,4-dimethylphenyl, 3-trifluoromethylphenyl, 4-methylphenyl, 3,4-difluorophenyl, 3-chloro-4-methylphenyl, 3-bromophenyl, 4-iodophenyl, 4-chlorophenyl, 2-chlorophenyl, 2-chloro-4-fluorophenyl, 3-isopropylphenyl, 4-ethylphenyl, 3-methoxycarbonylaminophenyl, 4-ethoxyphenyl, 2-methylphenyl, 3-methoxyphenyl, 4-cyanophenol, 2,6-dimethylphenyl, 2,4-dichlorophenyl, 3-methyl-4-chlorophenyl, 2-trifluoromethylphenyl, 2,4-dibromophenyl, 4-trifluoromethylphenyl, 4-methoxyphenyl, and 3-(1'-ethoxycarbonylethoxy)-phenyl), R⁵ and R⁶ being identical or different and each denoting hydrogen, unsubstituted or mono- or polysubstituted aryl, or one of the two substituents having the meanings given for R¹, and W, X, Y and Z are identical or different and each denotes hydrogen, alkyl (e.g., methyl), haloalkyl (e.g., trifluoromethyl), alkoxy (e.g., methoxy), halogen (fluoro, chloro, bromo, iodo), nitro or amino, have a good herbicidal action on numerous unwanted plants and are well tolerated by many crop plants. The new compounds also have a fungicidal action.

The new compounds may for example be prepared by the following methods; the radicals W, X, Y, Z, R¹, R², R³ and R⁴ have the above meanings. ##STR2##

This reaction scheme clearly illustrates the interrelationship between the starting materials. It is also clear that, depending on the nature of the substituents W, X, Y, Z, R¹, R², R³ and R⁴ and on the availability of the reactants, one route or another may be advantageous. The reaction of F to give H is preferred.

Starting from prior art meta-nitroanilines (A), meta-nitrophenyl isocyanates (B) may be prepared (W. Siefkin, J. Liebigs Annalen der Chemie, 562, 75 et seq., 1949) which in turn react smoothly with the hydroxy components R³ --OH to give the nitrourethanes (C) (S. Petersen, Methoden der Organ. Chemie, VIII, 131, Georg-Thieme-Verlag, Stuttgart, 4th ed., 1952), which are, however, also accessible direct from the meta-nitroanilines (A) and chloroformates (R³ O--CO--Cl) (German Laid-Open Application DOS 1,643,763). Subsequent reduction gives the amino compounds (F; R² ═H) (S. Schroter, Methoden der Organ. Chemie, XI/1, 360 et seq., Georg-Thieme-Verlag, Stuttgart, 4th ed., 1957) which are reacted, either direct or after conversion into the product mono-substituted on the amino nitrogen (F; R² ≠H) (Methoden der Organ. Chemie, XI/1, 24 et seq., Georg-Thieme-Verlag, Stuttgart, 4th ed., 1957) with chloroformates (R⁴ O--CO--Cl), to give the desired diurethanes (H) (German Laid-Open Application DOS 1,643,763). The aminourethanes (F) may also be obtained by reaction of meta-phenylenediamines (D) with chloroformates. A further synthesis possibility is the reaction of aryl-1,3-diisocyanates (E) with only 1 mole of the hydroxy component R³ --OH; this reaction gives the isocyanatourethanes (G) (J. A. Parker, J. J. Thomas and C. L. Zeise, J. Org. Chem., 22, 594-596, 1957), which are also obtainable by phosgenating the aminourethanes (F) (German Laid-Open Application DOS 1,914,270, p. 5, Ex. 8). Subsequent reaction with the hydroxyl component R⁴ OH gives the desired end products. In principle, the --COOR³ or --COOR⁴ groupings may be introduced in any order.

The preferred synthesis stages are described in more detail below:

(a) The 3-nitrophenyl isocyanates (B) are reacted with or without a catalyst usually used for isocyanate reactions, e.g., tertiary amines (triethylamine, 1,4-diazabicyclo-(2,2,2)-octane), nitrogenous heterocycles (pyridine, 1,2-dimethylimidazole) or organic tin compounds (dibutyl tin diacetate, dimethyl tin dichloride), in the presence or absence of a solvent inert under the reaction conditions, e.g., hydrocarbons (ligroin, naphtha, toluene, pentane, cyclohexane), halohydrocarbons (methyl chloride, chloroform, dichloroethane, chlorobenzene, o-, m- and p-dichlorobenzene), nitrohydrocarbons (nitrobenzene, nitromethane), nitriles (acetonitrile, butyronitrile, benzonitrile), ethers(diethyl ether, tetrahydrofuran, dioxane), esters (ethyl acetate, methyl propionate), ketones (acetone, methyl ethyl ketone) or amides (dimethylformamide, foramamide) (German Laid-Open Application DOS 1,568,138), at temperatures of from 0° to 150° C., preferably from 40° to 100° C.

(b) 3-nitroanilines (A) are reacted with a chloroformate in a suitable solvent, e.g., water, alcohols (methanol, ethanol, isopropanol) or those given under (a), with the additional employment of a conventional acid binder, e.g., alkali metal hydroxides, carbonates, bicarbonates, alkaline earth metal oxides, hydroxides, carbonates, bicarbonates, and tertiary organic bases (e.g., triethylamine, pyridine, N.N-dimethylaniline, N,N-dimethylcyclohexylamine, quinoline, tributylamine) or starting material 3-nitroaniline, at temperatures of from -20° to +150° C., preferably from +20° to 80° C.

(c) The nitrourethanes (C) may be reduced by one of the prior art processes, e.g., by catalytic hydrogenation, by a metal/acid combination, e.g., a combination of iron and acid, by a metal/alcohol combination, e.g., zinc dust/aqueous alcohol, iron/aqueous alcohol, etc.

(d) For the reaction of the m-phenylenediamines (D), comparable conditions as for (b) apply; it may, however, be advantageous to employ an excess of m-phenylenediamine.

(e) The aminourethanes F are reacted with chloroformates analogously to (b); the solution obtained for example by catalytic hydrogenation of the nitrourethanes C may also be employed direct without further purification.

The preparation of the new diurethanes and their precursors is illustrated by the following examples.

I Nitrourethanes EXAMPLE A

At 20° to 25° C. and while stirring, a mixture of 85 parts by weight of 3-nitrophenyl isocyanate and 43 parts by weight of toluene (absolute) is metered into a solution of 64.3 parts by weight of 4-chlorophenol and 3 parts by weight of triethylamine in 430 parts by weight of toluene (absolute).

To complete the reaction, the mixture was stirred for 1 hour at room temperature. After cooling to 0° C., the reaction product was suction filtered; m.p.: 137°-138° C.

The compound has the following structural formula: ##STR3##

EXAMPLE B

17.4 parts of sodium bicarbonate is added to 26 parts by weight of 3-nitro-N-methylaniline in 320 parts by weight of ethyl acetate. While stirring, 33 parts by weight of m-tolyl chloroformate is slowly added, the mixture is stirred for 20 hours at room temperature and filtered, the solvent is removed in vacuo, and the residue which remains is recrystallized from toluene/cyclohexane; m.p.: 114°-116° C.

The compound has the following structural formula: ##STR4##

The following nitrourethanes (C) may be prepared analogously:

    __________________________________________________________________________      ##STR5##                                                                      W   X    Y    Z    R.sup.1 R.sup.3           m.p. °C.                   __________________________________________________________________________     H   H    H    H    H       4-fluorophenyl    116-167                           H   H    H    H    H       1,4-dichlorophenyl                                  H   H    H    H    H       methyl            153-155                           H   CH.sub.3                                                                            H    H    H       methyl            132-133                           H   H    H    H    benzyl  4-chlorophenyl                                      H   H    H    H    H       phenyl            123-125                           H   H    H    H    H       3-methoxyphenyl                                     H   H    H    H    CH.sub.3                                                                               phenyl            60-70                             H   H    H    H    H       2-fluorophenyl    145-146                           H   F    H    H    H       phenyl            138-140                           H   H    H    H    H       3-bromophenyl     138                               H   H    H    H    CH.sub.3 OCH.sub.2                                                                     3-methylphenyl                                      H   H    H    H    H       3,4-dimethylphenyl                                                                               130-131                           H   H    CH.sub.3                                                                            H    H       methyl            86-87                             H   H    H    H    H       4-methoxyphenyl   132-133                           H   CH.sub.3                                                                            H    H    H       ethyl             131-133                           H   H    H    H    H       3-fluorophenyl    128-130                           H   H    H    H    H       ethyl             64-66                             CH.sub.3                                                                           H    H    H    H       phenyl            112-114                           H   H    H    H    H       2-chloro-4-fluorophenyl                                                                          146-147                           H   H    H    H    H       2-chlorophenyl    136-138                           H   F    H    F    H       methyl                                              H   H    H    H    C.sub.2 H.sub.5                                                                        4-cyanophenyl                                       H   H    H    CH.sub.3                                                                            H       methyl            114-117                           H   H    H    H    H       3-trifluoromethylphenyl                                                                          119-120                           Cl  H    Cl   H    CH.sub.3                                                                               2-methoxyethyl                                      H   H    H    H    H       4-trifluoromethylphenyl                             H   H    H    H    CH.sub.3                                                                               cyclodecyl                                          H   H    H    H    H       4-ethylphenyl     86-88                             H   H    H    Cl   H       phenyl            125-127                           H   H    H    H    H       3-chloro-4-fluorophenyl                             H   CH.sub.3                                                                            H    H    4-methyl-                                                                              methyl                                                                 benzyl                                                      H   H    H    H    H       2,4,6-trimethylphenyl                                                                            212-213                           H   H    H    Cl   H       methyl            122-124                           H   H    H    H    H       3,4-difluorophenyl                                  H   NO.sub.2                                                                            H    H    C.sub.2 H.sub.5                                                                        2,5-dichlorobenzyl                                  H   H    H    H    H                                                                                       ##STR6##         171-173                           H   H    H    CH.sub.3                                                                            H       ethyl             80-81                             H   H    H    H    H       cyclododecyl                                        H   H    H    H    H       3-isopropylphenyl 85-87                             H   H    H    H    C.sub.2 H.sub.5 OCH.sub.2                                                              n-butyl                                             H   H    H    H    H       2-trifluoromethylphenyl                             H   H    H    H    H       cyclooctyl        103-105                           H   H    H    H    H       4-methylphenyl    138-139                           H   H    H    H    H       2,4-dibromophenyl                                   H   H    H    H    H       tert.-butyl       97-99                             H   H    H    H    H       4-ethoxyphenyl                                      H   H    H    H    H       3-ethylphenyl     85-86                             H   H    H    H    CH.sub.3                                                                               cycloheptyl                                         H   H    H    H    H       2,6-dimethylphenyl                                                                               165-167                           H   H    CF.sub.3                                                                            H    H       isopropyl         121-123                           H   F    H    H    H       4-difluoromethoxyphenyl                             H   H    H    H    H       3-methoxycarbonyl-                                                                               172-174                                                      aminophenyl                                         H   H    H    H    H       2-methoxyphenyl                                     H   H    H    H    H       tricyclo-[4,3,1.sup.2,5 0.sup.1,6 ]-                                           decyl             103-105                           H   H    H    H    H       2-methylphenyl    126-128                           H   H    H    H    H       4-iodophenyl                                        H   H    H    H    CH.sub.3                                                                               methyl            54-56                             H   Cl   H    Cl   H       2-cyclohexylphenyl                                  H   H    H    H    H       3-methyl-4-chlorophenyl                             H   H    H    H    H       3,5-dimethylcyclohexyl                              H   H    H    H    H       1-naphthyl        141-142                           H   H    H    H    H       isopropyl         86-88                             H   Br   H    H    H       ethyl                                               H   H    H    H    H       4-nitrophenyl                                       H   F    H    H    H       methyl            116-118                           CH.sub.3                                                                           H    H    H    benzyl  ethyl                                               H   H    CF.sub.3                                                                            H    H       phenyl            133-135                           H   H    H    Br   CH.sub.3                                                                               methyl                                              H   H    H    H    H       2,6-dimethylcyclohexyl                                                                           121-123                           H   H    H    H    CH.sub.3 OCH.sub.3                                                                     3-fluorophenyl                                      H   OCH.sub.3                                                                           H    H    H       methyl            131-132                           CH.sub.3                                                                           H    H    H    CH.sub.3                                                                               benzyl                                              H   H    CF.sub.3                                                                            H    CH.sub.3                                                                               phenyl                                              H   H    H    H    H       cycloheptyl       102-104                           H   H    H    H    H       benzyl            113-115                           H   NO.sub.2                                                                            H    CH.sub.3                                                                            H       methyl                                              H   OCH.sub.3                                                                           H    H    H       phenyl            209-211                           H   H    H    H    H       3-methyl-5-isopropyl-                                                          phenyl                                              H   H    H    H    benzyl  n-butyl                                             H   H    H    H    H       norbornyl         118-120                           H   H    H    H    H       2-naphthyl                                          H   H    NO.sub.2                                                                            H    C.sub.2 H.sub.5                                                                        3-methylphenyl                                      H   H    H    H    H       cyclopentyl       110-112                           H   Cl   H    H    H       methyl            136-138                           H   H    H    H    iso-    4-methylthiophenyl                                                     propyl                                                      H   H    H    H    H       3-methylyclohexyl 120-122                           H   H    H    H    H       cyclohexyl        117-118                           H   H    H    H    H       2-methylcyclohexyl                                                                               100-102                           H   H    H    H    H       1,3-dimethoxyisopropyl                                                                           95-96                             H   H    H    H    H       3(N,N-dimethylamino)-                                                                            126-127                                                      phenyl                                              H   H    H    H    H       3,4-(tetramethylene)-                                                                            164-166                                                      phenyl                                              H   H    H    H    C.sub.2 H.sub.5                                                                        phenyl            56-58                             H   H    H    H    H       hexahydrobenzyl   127-128                           H   H    H    H    H       3,3,5-trimethylcyclo-                                                                            79-82                                                        hexyl                                               H   H    H    H    H       3-methyl-5-ethylphenyl                                                                           115-117                           H   H    H    H    H       tert-amyl         62-63                             H   H    H    H    H       2,3,6-trimethylphenyl                                                                            180-182                           H   H    H    H    H       2,3,5,6-tetramethyl-                                                                             237-238                                                      phenyl                                              H   H    H    H    H       4-tert-butylphenyl                                                                               113-115                           H   H    H    H    H       2,3,5-trimethylphenyl                                                                            145-147                           H   H    H    H    H       2-isopropyl-5-methyl-                                                                            103-105                                                      phenyl                                              H   H    H    H    H       2-tert-butyl-4-methyl-                                                                           154-156                                                      phenyl                                              H   H    H    H    H       2,6-dimethoxyphenyl                                                                              155-157                           H   H    H    H    H       3-methylphenyl    106-108                           H   H    H    H    C.sub.2 H.sub.5                                                                        3-methylphenyl    75-77                             H   H    H    H    H       2-methyl-6-isopropyl                                                                             122-124                           H   H    H    H    H       3,5-diethylphenyl 128-130                           __________________________________________________________________________

II Aminourethanes EXAMPLE C

3 parts of a hydrogenation catalyst (palladium on animal charcoal, 10%) was added to a solution of 135 parts by weight of 4-chlorophenyl N-(3-nitrophenyl)-carbamate in 900 parts by weight of tetrahydrofuran (absolute), and the mixture hydrogenated at room temperature and under a hydrogen pressure of 0.02 bar until the pressure no longer changes. The solution was freed from catalyst and dried with MgSO₄, and the solvent removed to such an extent that the crystalline reaction product was readily able to be suction filtered; m.p.: 186°-187° C. ##STR7##

EXAMPLE D

While stirring vigorously, 25.2 parts by weight of phenyl chloroformate was very slowly dripped into a solution of 108 parts by weight of m-phenylene diamine in 1,000 parts by weight of water. After the reaction was over, the mixture was suction filtered, the solid washed several times with dilute hydrochloric acid, and the combined acidic solutions were neutralized with ammonia and suction filtered. The dry product thus obtained melts with decomposition at 178°-180° C. Structure: ##STR8##

EXAMPLE E

While stirring vigorously, 130 parts by weight of 3-(O-phenylcarbamoyl)-nitrobenzene is added to a mixture, heated to 80° C., of 110 parts by weight of iron powder, 240 parts by weight of alcohol, 160 parts by weight of water and 7 parts by weight of concentrated hydrochloric acid in such portions that the temperature is kept at 80° C. without additional heating. The mixture is then refluxed for 1 hour and suction filtered while hot, the residue is digested with about 2,000 parts by weight of acetone, and twice the water is added to the combined filtrates before suction filtration is carried out; m.p. (after recrystallization from ethyl acetate): 180° C. (decomposes). ##STR9##

EXAMPLE F

While stirring vigorously, 52.1 parts by weight of phenyl chloroformate is dripped slowly into 51 parts by weight of 2,4-diaminonitrobenzene and 43 parts by weight of sodium bicarbonate in 600 parts by weight of tetrahydrofuran. The mixture is stirred for 14 hours and then filtered, and the residue is washed with tetrahydrofuran. The solution is freed from solvent to such a degree that the crystalline crude product is readily able to be suction filtered. After washing with diethyl ether and drying, the substance melts at 223°-225° C. According to the nmr spectrum and ultimate analysis, it has the following structure: ##STR10##

The following aminourethanes (F) may be prepared analogously:

    __________________________________________________________________________      ##STR11##                                                                     W   X    Y    Z    R.sup.1 R.sup.3           m.p. °                     __________________________________________________________________________                                                  C.                                H   H    H    H    H       4-fluorophenyl    166-167                           H   H    H    H    H       2,4-dichlorophenyl                                  H   H    H    H    H       methyl             87-89                            H   CH.sub.3                                                                            H    H    H       methyl            not                                                                            isolated                          H   H    H    H    benzyl  4-chlorophenyl                                      H   H    H    NO.sub.2                                                                            H       methyl            187-189                           H   H    H    H    H       3-methoxyphenyl                                     H   H    H    H    CH.sub.3                                                                               phenyl             68-70                            H   H    H    H    H       2-fluorophenyl    172-173                           H   F    H    H    H       phenyl            not                                                                            isolated                          H   H    H    H    H       3-bromophenyl                                       H   H    H    H    CH.sub.3 OCH.sub.2                                                                     3-methylphenyl                                      H   H    H    H    H       3,4-dimethylphenyl                                                                               155-157                           H   H    CF.sub.3                                                                            H    H       methyl            not                                                                            isolated                          H   H    H    H    H       4-methoxyphenyl   146-149                           H   CH.sub.3                                                                            H    H    H       ethyl             not                                                                            isolated                          H   H    H    H    H       3-fluorophenyl    decom-                                                                         position                          H   H    H    H    H       ethyl             not                                                                            isolated                          CH.sub.3                                                                           H    H    H    H       phenyl            131-133                           H   H    H    H    H       2-chloro-4-fluorophenyl                                                                          decom-                                                                         position                          H   H    H    H    H       2-chlorophenyl    decom-                                                                         position                          H   F    H    F    H       methyl            not                                                                            isolated                          H   H    H    H    C.sub.2 H.sub.5                                                                        4-Cyanophenyl                                       H   H    H    CH.sub.3                                                                            H       methyl            not                                                                            isolated                          H   H    H    H    H       3-trifluoromethylphenyl                                                                          126-128                           Cl  H    Cl   H    CH.sub.3                                                                               2-methoxyethyl                                      H   H    H    H    H       4-trifluoromethylphenyl                             H   H    H    H    CH.sub.3                                                                               cyclododecyl                                        H   H    H    H    H       4-ethylphenyl     160-161                           H   H    H    Cl   H       phenyl            215-217                           H   H    H    H    H       3-chloro-4-fluorophenyl                             H   CH.sub.3                                                                            H    H    4-methyl-                                                                              methyl                                                                 benzyl                                                      H   H    H    H    H       2,4,6-trimethylphenyl                                                                            150-152                           H   H    H    Cl   H       methyl                                              H   H    H    H    H       3,4-difluorophenyl                                  H   NO.sub.2                                                                            H    H    C.sub.2 H.sub.5                                                                        2,4-dichlorobenzyl                                  H   H    H    H    H                                                                                       ##STR12##        184-186                           H   H    H    CH.sub.3                                                                            H       ethyl             not                                                                            isolated                          H   H    H    H    H       cyclododecyl                                        H   H    H    H    H       3-isopropylphenyl  68-70                            H   H    H    H    C.sub.2 H.sub.5 OCH.sub.2                                                              n-butyl                                             H   H    H    H    H       2-trifluoromethylphenyl                             H   H    H    H    H       cyclooctyl         77-79                            H   H    H    H    H       4-methylphenyl    158-162                           H   H    H    H    H       2,4-dibromophenyl                                   H   H    H    H    H       tert-butyl        109-110                           H   H    H    H    H       4-ethoxyphenyl                                      H   H    H    H    H       3-ethylphenyl     112-114                           H   H    H    H    CH.sub.3                                                                               cycloheptyl                                         H   H    H    H    H       2,6-dimethylphenyl                                                                               160-161                           H   H    CF.sub.3                                                                            H    H       isopropyl         102-104                           H   F    H    H    H       4-difluoromethoxyphenyl                             H   H    H    H    H       3(O-methylcarbamoyl)-                                                                            149-151                                                      phenyl                                              H   H    H    H    H       2-methoxyphenyl                                     H   H    H    H    H       tricyclo-[4,3,1.sup.2,5 0.sup.1,6 ]-                                                             130-131                                                      decyl                                               H   H    H    H    H       2-methylphenyl    170-172                           H   H    H    H    H       4-iodophenyl                                        H   H    H    H    CH.sub.3                                                                               methyl            not                                                                            isolated                          H   Cl   H    Cl   H       2-cyclohexylphenyl                                  H   H    H    H    H       3-methyl-4-chlorophenyl                             H   H    H    H    H       3,5-dimethylcyclohexyl                              H   H    H    H    H       1-naphthyl        146-148                           H   H    H    H    H       isopropyl          66-68                            H   Br   H    H    H       ethyl                                               H   H    H    H    H       4-nitrophenyl                                       H   F    H    H    H       methyl            not                                                                            isolated                          CH.sub.3                                                                           H    H    H    benzyl  ethyl                                               H   H    CF.sub.3                                                                            H    H       phenyl            214-216                           H   H    H    Br   CH.sub.3                                                                               methyl                                              H   H    H    H    H       2,6-dimethylcyclohexyl                                                                           not                                                                            isolated                          H   H    H    H    CH.sub.3 OCH.sub.2                                                                     3-fluorophenyl                                      H   OCH.sub.3                                                                           H    H    H       methyl            not                                                                            isolated                          CH.sub.3                                                                           H    H    H    CH.sub.3                                                                               benzyl                                              H   H    CF.sub.3                                                                            H    CH.sub.3                                                                               phenyl                                              H   H    H    H    H       cycloheptyl        86-88                            H   H    H    H    H       benzyl            not                                                                            isolated                          H   NO.sub.2                                                                            H    CH.sub.3                                                                            H       methyl                                              H   OCH.sub.3                                                                           H    H    H       phenyl             84-86                            H   H    H    H    H       3-methyl-5-isopropyl-                                                                            not                                                          phenyl            isolated                          H   H    H    H    benzyl  n-butyl                                             H   H    H    H    H       nornornyl         150 -151                          H   H    H    H    H       2-naphthyl                                          H   H    NO.sub.2                                                                            H    C.sub.2 H.sub.5                                                                        3-methylphenyl                                      H   H    H    H    H       cyclopentyl       not                                                                            isolated                          H   Cl   H    H    H       methyl            not                                                                            isolated                          H   H    H    H    iso-    4-methylthiophenyl                                                     propyl                                                      H   H    H    H    H       3-methylcyclohexyl                                                                                95-97                            H   H    H    H    CH.sub.3                                                                               3-methylphenyl    114-115                           H   H    H    H    C.sub.2 H.sub.5                                                                        phenyl            104-106                           H   H    H    H    C.sub.2 H.sub.5                                                                        3-methylphenyl    104-105                           H   H    H    H    H       2-isopropyl-5-methyl-                                                                            122-123                                                      phenyl                                              H   H    H    H    H       3-methylphenyl    142-144                           H   H    H    H    H       2-tert-butyl-4-methyl-                                                                            89-91                                                       phenyl                                              H   H    H    H    H       tert-amyl          65-67                            H   H    H    H    H       hexahydrobenzyl   106-108                           H   H    H    H    H       3,4-(tetramethylene)-                                                                            181-183                                                      phenyl                                              H   H    H    H    H       3-methyl-5-ethylphenyl                                                                           102-104                           H   H    H    H    H       4-tert-butylphenyl                                                                               175-177                           H   H    H    H    H       2,3,5-trimethylphenyl                                                                            152-154                           H   H    H    H    H       2,3,6-trimethylphenyl                                                                            155-156                           H   H    H    H    H       3-(N,N-dimethylamine)-                                                                           132-133                                                      phenyl                                              H   H    H    H    H       3,5-diethylphenyl 121-123                           H   H    H    H    H       3,3,5-trimethylcyclo-                                                                             98-100                                                      hexyl                                               H   H    H    H    H       cyclohexyl        122-124                           H   H    H    H    H       2-methylcyclohexyl                                  H   H    H    H    H       1,3-dimethoxyisopropyl                              H   H    H    H    H       2-methyl-6-isopropyl-                                                                            133-135                                                      phenyl                                              __________________________________________________________________________      Note:                                                                          The amines termed "not isolated" were further reacted direct after             catalytic reduction without isolation and purification.                  

III Diurethanes EXAMPLE 1

11 parts by weight of sodium bicarbonate was added to a solution of 18.7 parts by weight of 4-chlorophenyl N-(3-aminophenyl)-carbamate in 125 parts by weight of tetrahydrofuran (absolute); subsequently, 9.4 parts by weight of methyl chloroformate was metered in at 20° to 25° C. and while cooling. To complete the reaction, the mixture was stirred for 1 hour at room temperature, after which it was filtered and the residue was concentrated in vacuo. The oily residue was dissolved in a small amount of ether and crystallized by adding petroleum ether; m.p.: 166°-167° C. (No. 1).

The compound has the following structural formula: ##STR13## The following compounds were prepared analogously;

    __________________________________________________________________________      ##STR14##                                                                     No.                                                                               W  X   Y  Z   R.sup.1                                                                               R.sup.2                                                                               R.sup.3         R.sup.4    m.p.                 __________________________________________________________________________                                                               °C.           2  H  H   H  H   H      H      phenyl          methyl     162-164              3  H  Cl  H  H   H      H      methyl          phenyl     133-135              4  H  H   H  H   H      H      2-fluorophenyl  ethyl      120-121              5  CH.sub.3                                                                          H   H  H   H      H      ethyl           phenyl     181-183              6  H  H   H  H   H      H      methyl          3-fluorophenyl                                                                            138-139              7  H  H   H  H   CH.sub.3                                                                              H      phenyl          methyl     142-143              8  H  H   H  H   H      H      4-fluorophenyl  methyl     154-155              9  H  H   H  Cl  H      H      phenyl          ethyl      147-149              10 H  H   H  H   H      CH.sub.3                                                                              ethyl           phenyl     150-152              11 H  H   H  H   H      H      ethyl           4-ethylphenyl                                                                              94-96               12 H  H   H  H   H      H      2,6-dimethyl-   allyl      100-103                                             cyclohexyl                                      13 H  H   H  H   CH.sub.3                                                                              H      3-methylphenyl  methyl     103-104              14 H  H   H  H   H      H      3-methoxycarbo- methyl     188-190                                             nylaminophenyl                                  15 H  H   H  H   H      H      isobutyl        phenyl     137-140              16 H  Cl  H  H   H      H      methyl          3-methylphenyl                                                                            154-156              17 H  H   H  H   H      H      ethyl           2,4-dichlorophenyl              18 H  H   H  H   H      H      2-fluorophenyl  methyl     176-177              19 H  H   H  H   benzyl H      methyl          4-chlorophenyl                  20 CH.sub.3                                                                          H   H  H   H      H      phenyl          methyl     164-166              21 H  H   H  H   H      H      methyl          3-methoxyphenyl                 22 H  H   H  H   H      H      ethyl           3-fluorophenyl                                                                            131-132              23 H  H   H  H   H      H      phenyl          ethyl      152-153              24 H  H   H  H   H      H      3-bromophenyl   methyl     168-170              25 H  H   H  H   H      CH.sub.3 OCH.sub.2                                                                    methyl          3-methylphenyl                  26 H  H   H  H   H      H      4-fluorophenyl  phenyl     161-164              27 H  H   H  H   H      H      2,4-dichlorophenyl                                                                             methyl     152-154              28 H  H   H  H   CH.sub.3                                                                              H      methyl          phenyl     oil                  29 H  H   H  H   H      H      4-methoxyphenyl methyl     165-166              30 H  H   H  H   H      H      methyl          3-ethylphenyl                                                                             106-107              31 H  H   H  H   H      H      3-methoxyphenyl ethyl                           32 H  H   H  H   H      H      phenyl          2-chloroethyl                                                                             118-120              33 H  H   H  H   H      H      ethyl           4-methoxyphenyl                                                                           142-143              34 H  H   H  H   H      H      methyl          3-(N,N-dimethyl-                                                                          169-171                                                             amino)-phenyl                   35 H  H   H  H   H      H      4-fluorophenyl  ethyl      129-132              36 H  H   H  H   H      H      5-indanyl       ethyl      101-103              37 H  H   H  H   H      H      2-chlorophenyl  methyl     170-171              38 H  H   H  H   C.sub.2 H.sub.5                                                                       H      4-cyanophenyl   methyl                          39 H  H   H  H   H      H      cyclopentyl     phenyl     158-160              40 Cl H   Cl H   CH.sub.3                                                                              H      2-methoxyethyl  1-naphthyl                      41 H  H   H  H   H      H      methyl          4-trifluoromethyl-                                                             phenyl                          42 H  H   H  H   H      H      2-methoxyethyl  4-fluorophenyl                                                                             95-97               43 H  H   H  H   H      CH.sub.3                                                                              methyl          cyclododecyl                    44 H  H   H  H   H      H      phenyl          isopropyl  114-115              45 H  H   H  H   H      H      ethyl           2-chlorophenyl                                                                            134-135              46 H  H   H  H   H      H      4-methylphenyl  ethyl      110-112              47 H  H   H  H   H      H      3-(N,N-dimethyl-                                                                               ethyl                                                          amino)-phenyl                                   48 H  H   H  H   H      H      ethyl           3-bromophenyl                   49 H  H   H  H   H      H      3-chloro-4-fluoro-                                                                             methyl                                                         phenyl                                          50 H  H   H  H   H      H      ethyl           4-chlorophenyl                                                                            146-148              51 H  H   H  H   H      H      4-trifluoromethyl-                                                                             ethyl                                                          phenyl                                          52 H  CH.sub.3                                                                           H  H   H      4-methyl-                                                                             phenyl          methyl                                                  benzyl                                                 53 H  H   H  Cl  H      H      methyl          4-methylthiophenyl              54 H  H   H  H   H      H      3-trifluoromethyl-                                                                             ethyl      113-115                                             phenyl                                          55 H  H   H  H   H      H      methyl          4-methylphenyl                                                                            187-189              56 H  H   H  H   H      H      3,4-difluorophenyl                                                                             ethyl                           57 H  NO.sub.2                                                                           H  H   C.sub.2 H.sub.5                                                                       H      2,4-dichlorobenzyl                                                                             methyl                          58 H  H   H  H   H      H      methyl          cyclododecyl                                                                              123-125              59 H  H   H  H   H      H      3-isopropylphenyl                                                                              ethyl       59-61               60 H  H   H  H   H      H      5-indanyl       methyl     152-154              61 H  H   H  H   H      C.sub.2 H.sub.5 OCH.sub.2                                                             methyl          n-butyl                         62 H  H   H  H   H      H      cyclododecyl    phenyl                          63 H  H   H  H   H      H      3-trifluoromethyl-                                                                             methyl     137-139                                             phenyl                                          64 H  H   H  H   H      H      cyclooctyl      ethyl                           65 H  H   H  H   H      H      methyl          3,4-difluorophenyl              66 H  H   H  H   H      H      methyl          3-isopropylphenyl                                                                          61-63               67 H  H   H  H   H      H      phenyl          cyclooctyl                      68 H  H   H  H   H      H      ethyl           3-ethylphenyl                                                                             oil                  69 H  H   H  H   H      H      3-chloro-4-fluoro-                                                                             ethyl                                                          phenyl                                          70 H  H   H  H   H      H      methyl          2,4-dibromophenyl               71 H  H   H  H   H      H      cyclopentyl     methyl     104-106              72 H  H   H  H   H      H      ethyl           cyclododecyl                    73 H  H   H  H   H      H      methyl          cyclooctyl oil                  74 H  H   H  H   H      H      3,4-dimethylphenyl                                                                             methyl      94-96               75 H  OCH.sub.3                                                                          H  H   H      H      methyl          phenyl     139-140              76 H  H   H  H   H      H      2-chloro-4-fluoro-                                                                             ethyl      130-132                                             phenyl                                          77 H  H   H  H   H      H      methyl          2,6-dimethylcyclo-                                                                        110-112                                                             hexyl                           78 H  H   H  H   H      H      ethyl           2,4-dibromophenyl               79 H  H   H  H   H      H      ethyl           3,4-dimethylphenyl                                                                        152-154              80 H  H   H  H   H      H      2-trifluoromethyl-                                                                             methyl                                                         phenyl                                          81 H  H   H  H   H      H      4-nitrophenyl   methyl                          82 H  H   H  H   H      H      cycloheptyl     methyl     117-119              83 H  H   H  NO.sub.2                                                                           H      H      methyl          phenyl     153-155              84 H  H   H  H   H      H      4-ethoxyphenyl  ethyl                           85 H  H   H  H   H      H      tert-butyl      methyl     116-118              86 H  H   H  H   CH.sub.3                                                                              H      cycloheptyl     propargyl                       87 H  H   H  H   H      H      methyl          2-chloro-4-fluoro-                                                                        170-172                                                             phenyl                          88 H  H   H  H   H      H      ethyl           2-trifluoromethyl-                                                             phenyl                          89 H  H   H  H   H      H      methyl          4-ethoxyphenyl                  90 H  H   H  H   H      H      norbornyl       methyl     110-112              91 H  H   H  H   H      H      ethyl           2,6-dimethylphenyl                                                                        118-120              92 H  H   H  H   H      H      2,4,6-trimethyl-                                                                               methyl     158-159                                             phenyl                                          93 H  H   H  NO.sub.2                                                                           H      H      phenyl          methyl     213-215              94 H  H   H  H   H      H      methyl          2,6-dimethylphenyl                                                                        133-134              95 H  H   H  H   H      H      4-ethylphenyl   methyl     148-150              96 H  F   H  H   H      H      4-difluoromethoxy-                                                                             methyl                                                         phenyl                                          97 H  H   H  H   H      H      benzyl          phenyl     140-142              98 H  H   H  H   H      H      methyl          2-methoxyphenyl                                                                           155-157              99 H  H   H  H   H      H      phenyl          tert-butyl 158-160              100                                                                               H  H   H  H   H      H      tricyclo-       methyl                                                         [4,3,1.sup.2,5 0.sup.1,6 ]-                                                    decyl                                           101                                                                               H  H   H  H   H      H      2-methylphenyl  ethyl      114-115              102                                                                               H  H   H  H   H      H      ethyl           2,4,6-trimethyl-                                                                          120-124                                                             phenyl                          103                                                                               H  H   H  NO.sub.2                                                                           H      H      n-butyl         methyl                          104                                                                               H  H   H  H   H      H      ethyl           tricyclo-                                                                      [4,3,1.sup.2,5 0.sup.1,6                                                       ]-                                                                             decyl                           105                                                                               H  H   H  H   H      H      methyl          benzyl     108-110              106                                                                               H  H   H  H   H      H      methyl          4-iodophenyl                    107                                                                               H  H   H  H   H      H      2-methylphenyl  methyl     158-159              108                                                                               H  H   H  H   H      CH.sub.3                                                                              ethyl           3-methylphenyl                                                                            101-102              109                                                                               H  H   H  H   H      H      2-methoxyphenyl ethyl                           110                                                                               H  H   H  H   H      H      tricyclo-       phenyl                                                         [4,3,1.sup.2,5 0.sup.1,6 ]-                                                    decyl                                           111                                                                               H  H   H  H   H      H      norbornyl       phenyl     190-192              112                                                                               H  H   H  H   H      H      ethyl           4-iodophenyl                    113                                                                               H  Cl  H  Cl  H      CH.sub.3                                                                              2-cyclohexylphenyl                                                                             methyl                          114                                                                               H  H   H  H   H      H      phenyl          n-propyl   159-161              115                                                                               H  H   H  H   H      H      methyl          3-methyl-4-chloro-                                                             phenyl     160-162              116                                                                               H  F   H  F   H      H      phenyl          methyl     164-166              117                                                                               H  H   H  H   H      H      3,5-dimethylcyclo-                                                                             ethyl                                                          hexyl                                           118                                                                               H  H   H  F   H      H      phenyl          methyl     119-122              119                                                                               H  H   H  H   H      H      propargyl       phenyl      92-94               120                                                                               H  H   H  H   H      H      methyl          1-naphthyl 174-175              121                                                                               H  Br  H  H   H      C1CH.sub.2                                                                            ethyl           phenyl                          122                                                                               H  H   H  H   H      H      3-methyl-5-iso- methyl      63-65                                              propylphenyl                                    123                                                                               H  H   H  H   H      H      methyl          3,5-dimethylcyclo-                                                                        112-119                                                             hexyl                           124                                                                               H  H   H  CH.sub.3                                                                           H      H      methyl          cyclohexyl 146-148              125                                                                               H  H   H  H   H      H      3-methyl-4-chloro-                                                                             ethyl                                                          phenyl                                          126                                                                               CH.sub.3                                                                          H   H  H   benzyl H      ethyl           cyclohexyl                      127                                                                               H  H   H  H   H      H      phenyl          allyl       90-93               128                                                                               H  H   H  H   H      H      2-naphthyl      methyl                          129                                                                               H  H   H  Br  CH.sub.3                                                                              H      methyl          4-chlorobutyn-                                                                 2-yl-1                          130                                                                               H  F   H  H   H      H      phenyl          methyl     133-135              131                                                                               H  H   H  H   CH.sub.3 OCH.sub.2                                                                    H      3-fluorophenyl  methyl                          132                                                                               H  H   H  H   H      H      ethyl           3-chlorophenyl                                                                            109-112              133                                                                               H  H   H  F   H      H      ethyl           phenyl     163-165              134                                                                               H  H   H  H   H      H      3,5-dimethylcyclo-                                                                             phenyl                                                         hexyl                                           135                                                                               H  H   CF.sub.3                                                                          H   H      CH.sub.3                                                                              methyl          phenyl                          136                                                                               H  NO.sub.2                                                                           H  CH.sub.3                                                                           H      H      methyl          4-fluorophenyl                  137                                                                               CH.sub.3                                                                          H   H  H   CH.sub.3                                                                              H      benzyl          propargyl                       138                                                                               H  H   H  H   H      H      phenyl          butyn-1-yl-3                                                                              117-119              139                                                                               H  H   H  H   CH.sub.3                                                                              H      3-methyl-5-iso- methyl                                                         propylphenyl                                    140                                                                               H  CH.sub.3                                                                           H  H   H      H      3-methylphenyl  methyl     155-157              141                                                                               H  H   H  H   H      benzyl sec-butyl       n-butyl                         142                                                                               H  H   NO.sub.2                                                                          H   C.sub.2 H.sub.5                                                                       H      3-methylphenyl  allyl                           143                                                                               H  H   H  CH.sub.3                                                                           H      H      methyl          3-chlorophenyl                                                                            168-170              144                                                                               H  H   H  H   H      H      isopropyl       3-methylphenyl                                                                            oil                  145                                                                               H  H   H  H   iso-   H      4-methylthiophenyl                                                                             n-propyl                                         propyl                                                        146                                                                               H  F   H  F   H      H      3-thiocyanatophenyl                                                                            methyl                          147                                                                               H  H   H  H   H      H      sec-butyl       phenyl     117-119              148                                                                               H  H   H  H   H      H      methyl          3-aminophenyl                   149                                                                               H  CH.sub.3                                                                           H  H   H      H      methyl          3-chlorophenyl                                                                            105-107              150                                                                               H  H   H  H   H      H      diphenyl        methyl                          151                                                                               H  H   H  H   H      H      3(N',N'-dimethyl-                                                                              allyl                                                          ureido)-phenyl                                  152                                                                               H  CH.sub.3                                                                           H  H   H      H      methyl          phenyl     147-149              153                                                                               H  F   H  F   H      CH.sub.3                                                                              methyl          3-phenoxyphenyl                 154                                                                               H  H   H  CH.sub.3                                                                           H      H      isopropyl       methyl     118-120              155                                                                               H  H   H  H   H      H      phenyl          n-butyl    108-110              156                                                                               H  CH.sub.3                                                                           H  H   H      H      ethyl           phenyl     170-172              157                                                                               H  H   H  H   H      H      3-methoxy-      methyl                                                         carbonylphenyl                                  158                                                                               H  H   H  H   H      H      methyl          n-decyl     85-87               159                                                                               H  CH.sub.3                                                                           H  H   H      H      phenyl          ethyl      146-148              160                                                                               H  H   H  H   H      H      4-phenoxyphenyl ethyl                           161                                                                               CH.sub.3                                                                          H   CH.sub.3                                                                          H   H      H      propargyl       (3-acetylamino)-                                                               phenyl                          162                                                                               H  H   H  H   H      H      phenyl          n-decyl     83-86               163                                                                               H  H   CF.sub.3                                                                          H   H      H      ethyl           phenyl      66-68               164                                                                               H  H   H  H   H      H      2-methoxyethyl  phenyl     oil                  165                                                                               H  H   H  H   H      H      methyl          4(CH.sub.3 SO.sub.2 )-pheny                                                    l                               166                                                                               H  H   H  H   H      H      3(CH.sub.3 SO.sub.3)-phenyl                                                                    ethyl                           167                                                                               H  H   CF.sub.3                                                                          H   H      H      methyl          phenyl      74-76               168                                                                               H  H   H  H   H      H      isopropyl       3-chlorophenyl                                                                            103-105              169                                                                               H  H   H  H   H      H      4-tert-butyl-   phenyl     161-163                                             cyclohexyl                                      170                                                                               H  H   H  H   H      H      phenyl          phenyl     175-176              171                                                                               H  H   H  H   H      H      ethyl           3-methylphenyl                                                                             76-78               172                                                                               H  H   H  H   H      H      methyl          4-tert-butyl-                                                                             oil                                                                 cyclohexyl                      173                                                                               H  H   CF.sub.3                                                                          H   H      H      3-methylphenyl  methyl      60-63               174                                                                               H  H   H  H   H      H      methyl          3-chlorophenyl                                                                            155-158              175                                                                               H  H   H  H   H      H      phenyl          2-ethyl-n-hexyl                                                                           oil                  176                                                                               H  H   H  H   H      H      cyclohexyl      phenyl     189-190              177                                                                               H  OCH.sub.3                                                                          H  H   H      H      phenyl          methyl     171-173              178                                                                               H  Cl  H  NO.sub.2                                                                           H      H      3-acetylphenyl  propargyl                       179                                                                               H  H   H  H   H      H      2-ethyl-n-hexyl methyl     oil                  180                                                                               H  H   H  OCH.sub.3                                                                          H      H      phenyl          ethyl      146-148              181                                                                               H  H   H  H   H      H      methyl          3-methylphenyl                                                                            137-139              182                                                                               H  H   H  H   H      H      4(CH.sub.3).sub.2 NSO.sub.2)-phenyl                                                            methyl                          183                                                                               H  H   H  H   H      H      3-methylcyclohexyl                                                                             methyl     137-139              184                                                                               H  H   H  H   H      H      cyclohexyl      methyl     128-130              185                                                                               H  H   H  H   H      H      methyl          propargyl   84-86               186                                                                               H  H   CF.sub.3                                                                          H   H      H      phenyl          isopropyl   75-77               187                                                                               H  H   H  H   H      H      methyl          3-(1'-ethoxycarbo-                                                             nylethoxy)-phenyl               188                                                                               H  H   H  CH.sub.3                                                                           H      H      2-chloropropen- 2-chloropropen-                                                                           103-104                                             (1)-yl-(3)      (1)-yl-(3)                      189                                                                               H  H   H  H   ethyl  H      methyl          phenyl                          190                                                                               H  CH.sub.3                                                                           H  H   H      H      1-chlorobutyn-  1-chlorobutyn-                                                                            117-118                                             (2)-yl-(4)      (2)-yl-(4)                      191                                                                               H  H   H  H   H      benzyl phenyl          methyl                          192                                                                               H  H   H  H   CH.sub.3                                                                              H      methyl          4-fluorophenyl                  193                                                                               H  H   H  H   H      H      methyl          methyl     161-163              194                                                                               H  H   H  H   H      H      n-butyl         methyl      70-72               195                                                                               H  H   NO.sub.2                                                                          H   H      CH.sub.3                                                                              allyl           4-benzoylphenyl                 196                                                                               H  H   H  H   H      H      methyl          methoxyethyl                                                                               76-79               197                                                                               H  H   H  H   H      H      1-naphthyl      ethyl      120-121              198                                                                               H  H   H  H   H      H      methyl          ethyl      116-118              199                                                                               H  H   H  H   H      C.sub.2 H.sub.5                                                                       methyl          3-methylphenyl                                                                            107-109              200                                                                               H  H   H  H   H      H      isopropyl       methyl     110-112              201                                                                               H  H   H  H   H      H      3-methyl-5-ethyl-                                                                              methyl     114-116                                             phenyl                                          202                                                                               H  H   H  H   C.sub.2 H.sub.5                                                                       H      phenyl          methyl     133-135              203                                                                               H  H   H  H   H      H      ethyl           3-methyl-5-ethyl-                                                                          87-89                                                              phenyl                          204                                                                               H  H   H  H   H      H      3,3,5-trimethyl-                                                                               methyl      64-67                                              cyclohexyl                                      205                                                                               H  H   H  H   H      H      3,4-(tetra-     methyl     149-151                                             methylenephenyl)                                206                                                                               H  H   H  H   H      H      ethyl           norbornyl   86-88               207                                                                               H  H   H  H   CH.sub.3                                                                              H      4-chlorophenyl  methyl     183-185              208                                                                               H  H   H  H   H      H      2-methyl-6-isopro-                                                                             methyl     127-129                                             pylphenyl                                       209                                                                               H  H   H  H   H      H      3-methylcyclohexyl                                                                             ethyl      oil                  210                                                                               H  H   H  H   H      H      3,5-diethylphenyl                                                                              methyl     113-115              211                                                                               H  H   H  H   H      H      2-isopropyl-5-  methyl     142-144                                             methylphenyl                                    212                                                                               H  H   H  H   H      H      ethyl           3,4-(tetra-                                                                                91-93                                                              methylene)-phenyl               213                                                                               H  H   H  H   H      H      methyl          2-tert-butyl-4-                                                                           166-168                                                             methylphenyl                    214                                                                               H  H   H  H   H      H      tert-amyl       methyl     152-154              215                                                                               H  H   H  H   H      H      methyl          hexahydrobenzyl                                                                            85-86               216                                                                               H  H   H  H   H      H      tert-butyl      ethyl       98-100              217                                                                               H  H   H  H   H      H      ethyl           isopropyl  117-119              218                                                                               H  H   H  H   H      H      cyclohexyl      ethyl      oil                  219                                                                               H  H   H  H   H      H      ethyl           2,6-dimethyl-                                                                             oil                                                                 cyclohexyl                      220                                                                               H  H   H  H   H      H      4-tert-butylphenyl                                                                             methyl     120-121              221                                                                               H  H   H  H   H      H      methyl          2,3,6-trimethyl-                                                                          167-169                                                             phenyl                          222                                                                               H  H   H  H   H      H      sec-butyl       methyl      92-94               223                                                                               H  H   H  H   H      H      2,3,5-trimethyl-                                                                               methyl     165-167                                             phenyl                                          224                                                                               H  H   H  H   CH.sub.3                                                                              H      methyl          methyl      62-63               225                                                                               H  H   H  H   H      CH.sub.3                                                                              methyl          2,4,6-trimethyl-                                                                          135-137                                                             phenyl                          226                                                                               H  H   H  H   H      H      methyl          butyn-1-yl-3                                                                              109-111              227                                                                               H  H   H  H   H      H      2,6-dimethoxyphenyl                                                                            methyl                          228                                                                               H  H   H  H   H      H      methyl          2,3,5,6-tetra-                                                                            214-216                                                             methylphenyl                    229                                                                               H  H   H  H   H      H      CH.sub. 3                                                                                       ##STR15## 105-107              230                                                                               H  H   H  H   H      H      CH.sub.3                                                                                        ##STR16## oil                  231                                                                               H  H   H  H   H      H      CH.sub.3                                                                                        ##STR17##                      232                                                                               H  H   H  H   H      H      CH.sub.3                                                                                        ##STR18##  84-86               233                                                                               H  H   H  H   H      H                                                                                      ##STR19##                                                                                      ##STR20## 111-113              234                                                                               H  H   H  H   H      H                                                                                      ##STR21##                                                                                      ##STR22## 131-133              235                                                                               H  H   H  H   H      H                                                                                      ##STR23##      CH.sub.2CHCH.sub.2                                                                         95-97               236                                                                               H  H   H  H   H      H                                                                                      ##STR24##                                                                                      ##STR25## oil                  237                                                                               H  H   H  H   CH.sub.3                                                                              H                                                                                      ##STR26##                                                                                      ##STR27## 134-136              238                                                                               H  H   H  H   C.sub.2 H.sub.5                                                                       H                                                                                      ##STR28##      C.sub.2 H.sub.5                                                                           135-137              239                                                                               H  H   H  H   H      H                                                                                      ##STR29##      CH.sub.3  CH.sub.3                                                             CH.sub.3   128-30               240                                                                               H  H   H  H   H      H                                                                                      ##STR30##      CH.sub.3  CH.sub.3                                                             CH.sub.3   163-165              241                                                                               H  H   H  H   H      H                                                                                      ##STR31##      CH.sub.3   168-170              242                                                                               H  H   H  H   H      H                                                                                      ##STR32##      CH.sub.3   167-168              243                                                                               H  H   H  H   H      H                                                                                      ##STR33##      CH.sub.3   162-164              244                                                                               H  H   H  H   H      H                                                                                      ##STR34##      CH.sub.3   138-140              245                                                                               H  H   H  H   H      H                                                                                      ##STR35##      CH.sub.3   131-133              246                                                                               H  H   H  H   H      H                                                                                      ##STR36##      CH.sub.3   115-118              247                                                                               H  H   H  H   H      H                                                                                      ##STR37##      CH.sub.3   137-139              248                                                                               H  H   H  H   H      H                                                                                      ##STR38##      CH.sub.3   118-120              249                                                                               H  H   H  H   H      H                                                                                      ##STR39##      CH.sub.3   152-154              250                                                                               H  H   H  H   H      H                                                                                      ##STR40##      CH.sub.3   179-181              251                                                                               H  H   H  H   H      H                                                                                      ##STR41##      CH.sub.3   130-132              252                                                                               H  H   H  H   H      H                                                                                      ##STR42##      CH.sub.3   117-119              253                                                                               H  H   H  H   H      H                                                                                      ##STR43##      CH.sub.3   127-129              254                                                                               H  H   H  H   H      H                                                                                      ##STR44##      C.sub.2 H.sub.5                                                                            70-72               255                                                                               H  H   H  H   H      H                                                                                      ##STR45##      CH.sub.3   151-152              256                                                                               H  H   H  H   H      H                                                                                      ##STR46##      CH.sub.3   145-147              257                                                                               H  H   H  H   H      H                                                                                      ##STR47##      CH.sub.3   oil                  258                                                                               H  H   H  H   H      H                                                                                      ##STR48##      CH.sub.3    74-76               259                                                                               H  H   H  H   H      H                                                                                      ##STR49##      CH.sub.3   212-214              __________________________________________________________________________

The herbicidal properties of some of the new compounds were examined under controlled conditions and in the open.

Greenhouse experiments

Plastic flowerpots having a volume of 300 cm³ were filled with a sandy loam. Seeds were then sown, or vegetatively reproduced species transplanted. The test plants were separated according to species. The active ingredients were suspended or emulsified in water as the vehicle and sprayed onto the surface of the soil by means of atomizing nozzles. After treatment, the vessels were lightly sprinkler-irrigated and then covered with transparent plastic hoods until the plants had taken root. For the postemergence (leaf) treatment, the plants were first grown to a height of from 3 to 10 cm, depending on habit, before being treated. The pots were of course not irrigated, and no hoods were placed on the pots. The plants were placed in either cooler or warmer parts of the greenhouse, depending on their temperature requirements. The experiments were run for from 2 to 4 weeks. During this period the plants were tended and their reaction to the individual treatments was assessed. The application rate of the compounds examined is given in kg/ha of active ingredient. For assessment, the 0 to 100 scale was used, 0 denoting no damage or normal emergence, and 100 denoting no emergence or complete destruction.

Experiments in climatic cabinets

Experiments were carried out in climatic cabinets of 1,000 liters volume, with selected agents and sugarbeets and mustard as test plants. The intensity of illumination was 10,000 lux, and the illumination duration 16 hours per day. The relative humidity was adjusted to 80%. Temperature ranges of 12° C. and 22° C. were kept separately so as to be able to ascertain the influence of temperature on the action of the agents.

The test plants were initially grown in the abovementioned pots in the greenhouse until 1 to 2 genuine leaves had developed. The plants were then treated as in the greenhouse experiments and transferred to the climatic cabinets. The observation periods lasted 3 weeks. The 0 to 100 scale was again employed for assessment.

Experiments in the open

Postemergence treatments were carried out on small plots. The compounds were applied, as an emulsion or suspension in water, with the aid of a motor-driven plot spray mounted on a hitch. All the experiments were observed for several weeks and again assessed on the 0 to 100 scale.

Results

The experiment carried out in accordance with the above methods gave the following results. The individual figures are contained in Tables 2 to 14.

1. In addition to a pronounced herbicidal action when applied to leaves, some of the new compounds had a noteworthy herbicidal effect when applied before the test plants had emerged (Tables 2, 11).

2. The herbicidal action on postemergence application was observed in numerous experiments with widely varying plant species from the most different botanical families (Tables 2 to 14). Prior art active ingredients gave in general poorer results than, and in some cases similar results to, the new active ingredients.

3. Numerous agricultural and horticultural crop plants suffered no appreciable damage, if any at all, after treatment with the new compounds (Tables 4, 5, 6, 7, 8, 9, 10, 12, 13); they may therefore be employed as selective herbicidal agents for controlling unwanted plant growth in a number of crop plants. Representatives of the new active ingredients are excellently suited for controlling weeds in soybeans (Table 12). Generally, the new compounds offered clear advantages over the prior art compounds in a wide variety of crops.

                  Table 1                                                          ______________________________________                                         List of test plants                                                                          Abbreviation                                                     Botanical name                                                                               in tables  Common name                                           ______________________________________                                         Alopecurus myosuroides                                                                       Alopec. myos.                                                                             slender foxtail                                                                (blackgrass)                                          Amaranthus retroflexus                                                                       Amar. ret. redroot pigweed                                       Anthemis spp. Anth.      chamomile                                             Arachis hypogaea                                                                             Arach. hyp.                                                                               peanuts (groundnuts)                                  Beta vulgaris --         sugarbeets                                            Bidens pilosa --         --                                                    Carthamus tinctorius                                                                         Carth. tinct.                                                                             safflower                                             Chenopodium album                                                                            Chen. alb. common lambsquarters                                  Centaurea cyanus                                                                             --         cornflower                                            Cucumis sativus                                                                              Cucum. sat.                                                                               cucumber                                              Daucus carota Dauc. car. carrots                                               Desmodium tortuosum                                                                          Desmod. tort.                                                                             Florida beggarweed                                    Echinochloa crus galli                                                                       Echin. c.g.                                                                               barnyardgrass                                         Galinsoga parviflora                                                                         Galin. par.                                                                               gallant soldier                                       Gylcine max.  Glyc. max. soybeans                                              Gossypium hirsutum                                                                           Gossyp. hirs.                                                                             cotton                                                Hordeum vulgare                                                                              Hord. vulg.                                                                               barley                                                Ipomoea spp.  Ipom. spp. morningglory                                          Lactuca sativa                                                                               Lac. sat.  lettuce                                               Lamium spp.   --         dead-hettle                                           Lolium multiflorum                                                                           --         annual ryegrass                                       Matricaria spp.                                                                              Matr.      chamomile                                             Matricaria inodora                                                                           Matr. inod.                                                                               false chemomile                                       Mercurialis annua                                                                            Merc. ann. annual mercury                                        Petroselinum spp.                                                                            Petr. spp. parsley                                               Polygonum persicaria                                                                         Poly. per. ladysthumb                                            Portulaca oleracea                                                                           Port. ol.  common purslane                                       Raphanua raphanistrum                                                                        Raph.      wild radish                                           Sesbania exaltata                                                                            Sesb. exalt.                                                                              hemp sesbania                                                                  (coffeeweed)                                          Setaria viridis                                                                              Set. vir.  green foxtail                                         Setaria faberii                                                                              --         giant foxtail                                         Sinapis alba  Sinap. alba                                                                               white mustard                                         Solanum nigrum                                                                               --         black nightshade                                      Spergula arvensis                                                                            Sperg. arv.                                                                               corn spurry                                           Stellaria media                                                                              Stel. med. chickweed                                             Thlaspi arvense                                                                              Thlas. arven.                                                                             field pennycress                                      Triticum aestivum                                                                            Tritic. aest.                                                                             wheat                                                 Xanthium pensylvanicum                                                                       Xanth. pens.                                                                              common cocklebur                                      Zea mays      --         Indian corn                                           ______________________________________                                    

                  Table 2                                                          ______________________________________                                         Herbicidal action of some new compounds;                                       preemergence treatment in the greenhouse                                       Active                                                                         ingredient         Test plants and % damage                                    no.       kg/ha    Sesbania exaltata                                                                            Sinapis alba                                  ______________________________________                                         23        3.0      --             80                                           13        3.0      --            100                                            8        3.0      100           --                                            46        3.0       90           --                                             7        2.0      --            100                                           ______________________________________                                          0 = no damage?                                                                 100 = no emergence or plants destroyed?                                  

                                      Table 3                                      __________________________________________________________________________     Herbicidal action of some new compounds; postemergence treatment in the        open                                                                           Active    Test plants and % damage                                             ingredient                                                                               Alopec.                                                                             Anth./                                                                             Chen.                                                                              Echin.                                                                             Galin.                                                                             Poly.                                                                             Raph./                                                                             Sperg.                                                                             Thlas.                               no.   kg/ha                                                                              myos Matr.                                                                              alb.                                                                               c.g.                                                                               par.                                                                               per.                                                                              Sina.                                                                              arv.                                                                               arven.                               __________________________________________________________________________      2    0.5 35   45  100 50   98  95                                                                                98 100 62                                         1.0 65   78  100 75  100 100                                                                                98 100 75                                         2.0 90   88  100 90  100 100                                                                               100 100 80                                    7    0.5 30    8  100 45   92  90                                                                                80 100 93                                         1.0 50   10  100 65   98 100                                                                                95 100 100                                        2.0 70   20  100 72   98 100                                                                                98 100 100                                  181   0.5 50   52  100 58  100  85                                                                               100 100 80                                         1.0 70   78  100 80  100 100                                                                               100 100 95                                         2.0 85   92  100 95  100 100                                                                               100 100 100                                  __________________________________________________________________________      0 = no damage                                                                  100 = plants destroyed                                                   

                                      Table 4                                      __________________________________________________________________________      Selective herbicidal action of various compounds;                             postemergence treatment in the greenhouse                                      __________________________________________________________________________     Active                            Test plants and % damage                     ingredient                        Arach.                                                                             Cucum.                                                                              Dauc.                                                                              Glyc.                                                                             Petr.                        no.                           kg/ha                                                                              hyp.                                                                               sat. car.                                                                               max                                                                               spp.                         __________________________________________________________________________     35                            2.0 0   10    0   0  0                            ##STR50##                    2.0 0   40   20  20 40                           prior art                                                                      __________________________________________________________________________     Active                        Test plants and % damage                         ingredient                    Amar.                                                                              Chen.                                                                              Merc.                                                                              Sesb.                                                                             Sinap.                                                                             Stell.                        no.                       kg/ha                                                                              ret.                                                                               alb.                                                                               ann.                                                                               exalt                                                                             alba                                                                               media                         __________________________________________________________________________     35                        2.0 100 95   90 75  95 95                             ##STR51##                2.0  98 95  100 85 100 70                            prior art                                                                      __________________________________________________________________________      0 = no damage                                                                  100 = plants destroyed                                                   

                                      Table 5                                      __________________________________________________________________________     Selective herbicidal action of various compounds;                              postemergence treatment in the greenhouse                                      Active              Test plants and % damage                                   ingredient          Arach.                                                                             Glyc.                                                                              Gossyp.                                                                            Desmod.                                                                             Sesb.                                                                              Xanth.                                no.             kg/ha                                                                              hyp.                                                                               max.                                                                               hirs.                                                                              tort.                                                                               exalt.                                                                             penns.                                __________________________________________________________________________     2               1.0 0   15   0  78    90 20                                                    2.0 0   15  10  78    90 80                                     ##STR52##      1.0 2.0                                                                            0 0 30 30                                                                              10 20                                                                               5 70                                                                               100 100                                                                            10 30                                 prior art                                                                       ##STR53##      1.0 2.0                                                                            0 0  0  0                                                                              70 70                                                                               0  0                                                                               100 100                                                                            90 90                                 prior art                                                                      __________________________________________________________________________      0 = no damage                                                                  100 = plants destroyed                                                   

                                      Table 6                                      __________________________________________________________________________     Selective herbicidal action of various compounds;                              postemergence treatment in the greenhouse                                      __________________________________________________________________________     Active                             Test plants and % damage                    ingredient                         Arach.                                                                             Cucum.                                                                              Dauc.                                                                              Gossyp.                                                                            Petr.                      no.                            kg/ha                                                                              hyp.                                                                               sat. car.                                                                               hirs.                                                                              spp.                       __________________________________________________________________________      7                             0.5 --   0    0  20   0                                                        1.0  0  --   10  20   0                          2                             0.5 --  20    0   0   0                                                        1.0 10  20    0  10   0                         181                            0.5 --  20    0  20   0                                                        1.0 10  20    0  40   0                          ##STR54##                     0.5 1.0                                                                            --  0                                                                              40 50                                                                               35 45                                                                              25 45                                                                              10 85                      prior art                                                                      __________________________________________________________________________     Active                        Test plants and % damage                         ingredient                    Amar.                                                                              Ipom.                                                                              Merc.                                                                              Port.                                                                             Sesb.                                                                             Set.                                                                              Sinap.                      no.                       kg/ha                                                                              ret.                                                                               spp.                                                                               ann.                                                                               ol.                                                                               exalt                                                                             vir.                                                                              alba                        __________________________________________________________________________      7                        0.5  65  95 70   95                                                                                95                                                                                70                                                                                60                                                   1.0  75 100 70  100                                                                                95                                                                               100                                                                               100                          2                        0.5  70  80  0  100                                                                                35                                                                               100                                                                                95                                                   1.0 100  80  0  100                                                                               100                                                                               100                                                                               100                         181                       0.5  55 100 95   90                                                                                55                                                                                90                                                                               100                                                   1.0  65 100 95   90                                                                               100                                                                               100                                                                               100                          ##STR55##                0.5 1.0                                                                             0  10                                                                              40 30 30                                                                              100 100                                                                            90 100                                                                            90  95                                                                            92  98                     prior art                                                                      __________________________________________________________________________      0 = no damage                                                                  100 = plants destroyed                                                   

                                      Table 7                                      __________________________________________________________________________     Herbicidal action and tolerance by crop plants of various compounds,           postemergence treatment in the greenhouse                                      __________________________________________________________________________     Active                                 Test plants and % damage                ingredient                             Arach.                                                                             Glyc.                                                                             Hord.                                                                              Lact.                        no.                                kg/ha                                                                              hyp.                                                                               max.                                                                              vulg.                                                                              sat.                         __________________________________________________________________________     184                                2.0 0    0  0   0                            ##STR56##                         2.0 0   10 25  30                           prior art                                                                       ##STR57##                         2.0 0    0  0  90                           prior art                                                                      __________________________________________________________________________     Active                        Test plants and % damage                         ingredient                    Tritic.                                                                            Amar.                                                                              Chen.                                                                              Sesb.                                                                             Sinap.                                                                             Stell.                        no.                       kg/ha                                                                              aest.                                                                              ret.                                                                               alb.                                                                               exalt                                                                             alba                                                                               media                         __________________________________________________________________________     184                       2.0 0   80  80  100                                                                                90 80                             ##STR58##                2.0 60  30  95   90                                                                               100 90                            prior art                                                                       ##STR59##                                                                                               2.0 0   20  95   85                                                                               100 95                            prior art                                                                      __________________________________________________________________________      0 = no damage                                                                  100 = plants destroyed                                                   

                                      Table 8                                      __________________________________________________________________________     Selective herbicidal action of various compounds;                              postemergence treatment in the greenhouse                                      Active                        Test plants and % damage                         ingredient                    Arach.                                                                             Glyc.                                                                             Amar.                                                                              Merc.                                                                              Port.                                                                              Sesb.                                                                             Set.                                                                               Sinap.                                                                            Stell.              no.                       kg/ha                                                                              hyp.                                                                               max.                                                                              ret.                                                                               ann.                                                                               ol.                                                                               exalt.                                                                             vir.                                                                              alba                                                                               media               __________________________________________________________________________     13                        0.5 --  10  45 95  100                                                                               100  85                                                                               100 90                                            1.0 10  10  50 95  100                                                                               100  85                                                                               100 90                  8                         0.5 --   0  98 40  100                                                                                70 100                                                                                50 80                                            1.0  0   0 100 70  100                                                                                70 100                                                                                50 80                   ##STR60##                0.5 1.0                                                                            --  0                                                                               0  0  10                                                                             60 60                                                                              100 100                                                                            90  90  90                                                                            90 90 90               prior art                                                                       ##STR61##                0.5 1.0                                                                            --  0                                                                               0  0  10                                                                             40 80                                                                              100  --                                                                            85  10  40                                                                           100 100                                                                            95 95               prior art                                                                      __________________________________________________________________________      0 = no damage                                                                  100 = plants destroyed                                                   

                                      Table 9                                      __________________________________________________________________________     Tolerance by sugarbeets and herbicidal action of various compounds;            postemergence treatment in climatic cabinet                                                             Test plants and                                                                % damage                                              Active                   Temperature ranges °C.                         ingredient               Sugarbeets                                                                           Sinapis alba                                    no.                  kg/ha                                                                              11 22 11 22                                           __________________________________________________________________________     2                    0.5  0  0 70  92                                                               1.0 12  2 75  92                                                               2.0 10  2 85 100                                           ##STR62##           0.5 1.0 2.0                                                                         0 10 10 10                                                                          88 90 90                                                                           95 100 100                                  __________________________________________________________________________      0 = no damage                                                                  100 = plants destroyed                                                   

                                      Table 10                                     __________________________________________________________________________     Selective herbicidal action of new diurethanes; postemergence treatment        in the greenhouse                                                               ##STR63##                                                                     Active                Test plants and % damage                                 ingredient                                                                              Substituent  Arach.                                                                             Carth.                                                                             Dauc.                                                                              Hord.                                                                              Tritic                                                                             Zea Desmod.                                                                              Sesb.                                                                              Sinap.                                                                             Stell.             no.      R       kg/ha                                                                               hyp.                                                                               tinct.                                                                             car.                                                                               vulg.                                                                              aest.                                                                              mays                                                                               tort.                                                                               exalt.                                                                             alba.                                                                              med.                __________________________________________________________________________      ##STR64##       1.0 2.0                                                                             10 20                                                                              0 0 0 0 0 0 0 0 10 15                                                                              100 100                                                                             90 95                                                                              99 99                                                                               30  70              90              1.0   0  0   0   0   0    0  100  95   75 100                                  2.0   0  0   0   0   0    0  100  95   95 100                  82              1.0   0  0   0   0   0    0  100  95   99 100                                  2.0   0  0   0   0   0    0  100  95  100 100                 105              1.0   0  0   0   --  0    0  100  45  100 --                                   2.0   0  0   0   --  0    0  100  50  100 --                  172              1.0   0  0   --  0   --   0   30  50   60 100                                  2.0  20  0   --  0   0    0  100  60  100 --                  __________________________________________________________________________      0 = no damage                                                                  100 = plants destroyed                                                   

                                      Table 11                                     __________________________________________________________________________     Preemergence action of new diurethanes; greenhouse application                 Active                                Test plants and % damage                 ingredient                            Amar.                                                                              Bidens                                                                             Matr.                                                                              Sinap.                                                                             Solanum                                                                             Stell.              no.    Compounds                 kg/ha                                                                               ret.                                                                               pilosa                                                                             inod.                                                                              alba                                                                               nigrum                                                                              med.                __________________________________________________________________________     85                               1.0  90  100 100 98  65   98                                                   2.0  95  100 100 98  90   98                          ##STR65##                1.0 2.0                                                                              0  0                                                                               10  40 40 50                                                                              10 15                                                                               50 70                       ##STR66##                1.0 2.0                                                                             60 80                                                                               95 100 100                                                                            95 95                                                                              55 70                                                                               60 70               __________________________________________________________________________      0 = no damage                                                                  100 = plants destroyed                                                   

                                      Table 12                                     __________________________________________________________________________     Tolerance by various soybean species; postemergence application in the         greenhouse                                                                     Active                                                                         ingred-                % damage in soybean species and other test plants       ient                   SRF                         Setaria.sup.x                                                                      Sesb..sup.x                                                                        Stell.              no. Compound       kg/ha                                                                              450                                                                               Dare                                                                              Lee 68                                                                             Bragg                                                                              Prata                                                                              Prenola                                                                             Planato                                                                              faberii                                                                           exalt.                                                                             media               __________________________________________________________________________     8                  0.5 0   0 0   0   0   0    0    10  60   40                 8   + linseed oil emulsi-                                                                         0.5 0  10 0   15  0   0    0    100 95  100                     fied in water in                                                               amount of 4 vol %                                                              of spray liquor                                                                 ##STR67##     0.5 0   0 0   0   0   0    0    0   40  100                      ##STR68##     0.5 0  10 0   0   10  10   10   0   80  100                     + linseed oil emulsi-                                                          fied in water in                                                               amount of 4 vol %                                                              of spray liquor                                                            __________________________________________________________________________      0 = no damage                                                                  100 = plants destroyed                                                         .sup.x = larger plants than in Table 8                                   

                                      Table 13                                     __________________________________________________________________________     Selective herbicidal action in beets; postemergence treatment                  in the greenhouse                                                              Active          Test plants and % damage                                       ingredient      Beta                                                                              Hord.                                                                              Chen.                                                                              Lamium                                                                              Merc.                                                                              Sinapis                                    no.   Compound                                                                             kg/ha                                                                              vulg.                                                                             vulg.                                                                              alb.                                                                               spp. annua                                                                              alba                                       __________________________________________________________________________                 1.0 0  0   80  100   80  98                                                    2.0 0  0   --  100  100 100                                        101                                                                            __________________________________________________________________________      0 = no damage                                                                  100 = plants destroyed                                                   

                  Table 14                                                         ______________________________________                                         Herbicidal action of new compounds, preemergence (PRE) and                     postemergence (POST) treatment in greenhouse                                               Test plants and % damage                                           Active                             Lolium                                      ingredient        Centaurea Ipomoea                                                                               multi-                                                                               Sinapis                               no.     kg/ha     cyanus    spp.   florum                                                                               alba                                  ______________________________________                                                 3.0 PRE   --        0      0     100                                   204     3.0 POST  100       0      95    --                                            3.0 PRE   --        0      10    80                                    209     3.0 POST  100       100    40    --                                            3.0 PRE   --        0      0      0                                    205     3.0 POST  80        80     40     0                                            3.0 PRE   --        0      0      0                                    212     3.0 POST  80        20     40    --                                            3.0 PRE   --        0      0     40                                    199     3.0 POST  80        60     40    --                                            3.0 PRE   --        40     80    80                                    202     3.0 POST  80        80     80    --                                            3.0 PRE   --        0      20    0                                     201     3.0 POST  80        80     80    --                                            3.0 PRE   --        80     50    40                                    216     3.0 POST  100       100    90    --                                    ______________________________________                                          0 = no damage                                                                  100 = plants destroyed                                                   

The new active ingredients may be incorporated into the soil, or applied to the surface of the soil or to emerged plants. It is also possible to eliminate unwanted plants by post-directed or lay-by applications. In this case, the spray is directed in such a manner that the leaves of sensitive crop plants are not--or only slightly--touched, and the soil and smaller weeds are fully contacted.

In view of the application possibilities, the herbicides according to the invention or compositions containing them may not only be used in the crops listed in the tables but also in a much wider range of crops for removing unwanted plants. The amount of active ingredient applied may vary from 0.1 to 15 kg/ha and more, depending on the weeds to be controlled. The following crops may be mentioned by way of example:

    ______________________________________                                         Botanical name       Common name                                               ______________________________________                                         Allium cepa              onions                                                Ananas comosus           pineapple                                             Asparagus officinalis    asparagus                                             Avena sativa             oats                                                  Beta vulgaris spp. rapa  fodder beets                                          Beta vulgaris spp. esculenta                                                                            table beets, red beets                                Brassica napus var. napus                                                                               rape                                                  Brassica napus var. napobrassica                                               Brassica napus var. rapa turnips                                               Brassica rapa var. silvestis                                                   Camellia sinensis        tea plants                                            Carthamus tinctorius     safflower                                             Citrus limon             lemon                                                 Citrus maxima            grapefruit                                            Citrus reticulata                                                              Citrus sinensis          orange trees                                          Coffea arabica (Coffea canephora,                                                                       coffee plants                                         Coffea liberica)                                                               Cucumis melo             melons                                                Cynodon dactylon         Bermudagrass in turf                                                           and lawns                                             Elaeis guineensis        oil palms                                             Fragaria vesca           strawberries                                          Gossypium arboreum                                                             Gossypium herbaceum      cotton                                                Gossypium vitifolium                                                           Helianthus annuus        sunflowers                                            Helianthus tuberosus                                                           Hevea brasiliensis       rubber plants                                         Humulus lupulus          hops                                                  Ipomoea batatas          sweet potato                                          Lens culinaris           lentils                                               Linum usitatissimum      flax                                                  Lycopersicon lycopersicum                                                                               tomato                                                Malus spp.               apple trees                                           Manihot esculenta        cassava                                               Medicago sativa          alfalfa (lucerne)                                     Mentha piperita          peppermint                                            Musa spp.                banana plants                                         Nicotiana tabacum        tobacco                                               (N. rustica)                                                                   Olea europaea            olive trees                                           Oryza sativa             rice                                                  Panicum miliaceum                                                              Phaseolus lunatus        limebeans                                             Phaseolus mungo          mungbeans                                             Phaseolus vulgaris       snapbeans, green beans,                                                        dry beans                                             Pennisetum glaucum                                                             Picea abies                                                                    Pinus                    pine trees                                            Pisum sativum spp. sativum                                                                              English peas                                          Prunus avium             cherry trees                                          Prunus domestica         plum trees                                            Prunus persica           peach trees                                           Pyrus communis           pear trees                                            Ribes sylvestre          redcurrants                                           Ribes uva-crispa                                                               Ricinus communis                                                               Saccharum officinarum    sugar cane                                            Secale cereale           rye                                                   Solanum tuberosum        Irish potatoes                                        Sorghum bicolor (S. vulgare)                                                                            grain sorghum                                         Sorghum dochna                                                                 Spinacia oleracea        spinach                                               Theobroma cacao          cacao plants                                          Trifolium pratense       red clover                                            Vaccinium corymbosum     blueberry                                             Vaccinium vitis-idaea    cranberry                                             Vicia faba               tick beans                                            Vigna sinensis (V. unguiculata)                                                                         cow peas                                              Vitis vinifera           grapes                                                Zea mays                 Indian corn, sweet corn,                                                       maize                                                 ______________________________________                                    

To broaden the spectrum of action of the new individual compounds, to achieve synergistic effects or to improve persistence in the soil, the compounds according to the invention may be mixed with each other, and numerous other herbicidal and growth-regulating compounds may be used as mixture and combination components. Depending on area of use and objective, the following substances or similar derivatives may be used in mixtures:

    __________________________________________________________________________      ##STR69##                                                                     R                   R.sup.1                                                    __________________________________________________________________________      ##STR70##          NH.sub.2                                                    ##STR71##          NHCH.sub.3                                                  ##STR72##          NHCH.sub.3                                                  ##STR73##          NH.sub.2                                                   __________________________________________________________________________      ##STR74##                                                                     R                   R.sup.1      R.sup.2                                       __________________________________________________________________________                          ##STR75##   H and salts                                   H                                                                                                   ##STR76##   Cl and salts                                  H                                                                                                   ##STR77##   F and salts                                   H                                                                                                   ##STR78##   CH.sub.3 and salts                            CH.sub.2 OCH.sub.3                                                                                  ##STR79##   H                                             __________________________________________________________________________      ##STR80##                                                                      ##STR81##                                                                     R.sup.1             R.sup.2      R.sup.3                                       __________________________________________________________________________     CF.sub.3            n . C.sub.3 H.sub.7                                                                         n . C.sub.3 H.sub.7                           CF.sub.3            n . C.sub.3 H.sub.7                                                                         CH.sub.2CH.sub.2 Cl                           SO.sub.2 NH.sub.2   n . C.sub.3 H.sub.7                                                                         n . C.sub.3 H.sub.7                           __________________________________________________________________________      ##STR82##                                                                     R.sup.1             R.sup.2      R.sup.3                                       __________________________________________________________________________     CH.sub.3            H                                                                                            ##STR83##                                     ##STR84##          H            i-C.sub.3 H.sub.7                              ##STR85##          H                                                                                            ##STR86##                                     ##STR87##          H                                                                                            ##STR88##                                     ##STR89##          H            i-C.sub. 3 H.sub.7                             ##STR90##          H            CH.sub.2CCCH.sub.2 Cl                          ##STR91##          H                                                                                            ##STR92##                                     ##STR93##          H            CH.sub.3                                       ##STR94##          H            CH.sub.3                                      __________________________________________________________________________      ##STR95##                                                                      ##STR96##                                                                     R.sup.1             R.sup.2      R.sup.3                                       __________________________________________________________________________      ##STR97##          H            C.sub.2 H.sub.5                                ##STR98##          CH.sub.3     CH.sub.3                                      __________________________________________________________________________      ##STR99##                                                                     R.sup.1             R.sup.2      R.sup.3                                       __________________________________________________________________________      ##STR100##         H            CH.sub.3                                       ##STR101##         H            C.sub.2 H.sub.5                                ##STR102##         H            CH.sub.3                                       ##STR103##         H            C.sub.2 H.sub.5                               __________________________________________________________________________      ##STR104##                                                                    R.sup.1             R.sup.2      R.sup.3                                       __________________________________________________________________________     i-C.sub.3 H.sub.7   i-C.sub.3 H.sub.7                                                                           CH.sub.2CClCHCl                               n . C.sub.3 H.sub.7 n . C.sub.3 H.sub.7                                                                         C.sub.2 H.sub.5                               n . C.sub.3 H.sub.7 n . C.sub.3 H.sub.7                                                                         n . C.sub.3 H.sub.7                           sec. C.sub.4 H.sub.9                                                                               sec. C.sub.4 H.sub.9                                                                        C.sub.2 H.sub.5                               C.sub.2 H.sub.5     C.sub.2 H.sub.5                                                                              ##STR105##                                    ##STR106##         C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                ##STR107##         C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                               __________________________________________________________________________      ##STR108##                                                                     ##STR109##                                                                    __________________________________________________________________________     C.sub.2 H.sub.5                                                                n . C.sub.3 H.sub.7                                                             ##STR110##                                                                    __________________________________________________________________________      ##STR111##                                                                    R.sup.1             X            Y          R.sup.2                            __________________________________________________________________________     CH.sub.3            Cl           Cl         Na                                 Cl                  Cl           Cl         Na                                 C.sub.2 H.sub.5     Cl           Cl         Na                                  ##STR112##         Cl           H          CH.sub.3                            ##STR113##         H            H          H and salts                         ##STR114##         H            Cl         NH.sub.4                            ##STR115##         H            CH.sub.3   C.sub.2 H.sub.5                     ##STR116##         H            CH.sub.3   CH.sub.3                            ##STR117##         H            CH.sub.3   i-C.sub.3 H.sub.7                   ##STR118##         H            CH.sub.3                                                                                   ##STR119##                         ##STR120##         H            CH.sub.3   CH.sub.3                           __________________________________________________________________________      ##STR121##                                                                     ##STR122##                                                                     ##STR123##                                                                     ##STR124##                                                                    R.sup.1             X            R.sup.2                                       __________________________________________________________________________     i-C.sub.3 H.sub.7   Cl           C.sub.2 H.sub.5                               i-C.sub.3 H.sub.7   Cl                                                                                           ##STR125##                                   i-C.sub.3 H.sub.7   Cl           i-C.sub.3 H.sub.7                             C.sub.2 H.sub.5     Cl           C.sub.2 H.sub.5                               C.sub.2 H.sub.5     Cl           C(CH.sub.3).sub.2 CN                          C.sub.2 H.sub.5     Cl                                                                                           ##STR126##                                   C.sub.2 H.sub.5     Cl                                                                                           ##STR127##                                    ##STR128##         Cl           C(CH.sub.3).sub.2CN                           i-C.sub.3 H.sub.7   OCH.sub.3    i-C.sub.3 H.sub.7                             i-C.sub.3 H.sub.7   SCH.sub.3    C.sub.2 H.sub.5                               C.sub.2 H.sub.5     SCH.sub.3    C.sub.2 H.sub.5                               C.sub.2 H.sub.5     SCH.sub.3    tert. C.sub.4 H.sub.9                         __________________________________________________________________________      ##STR129##                                                                    X                   Y            R                                             __________________________________________________________________________     CF.sub.3            H            CH.sub.3                                      H                   F            CH.sub.3                                      __________________________________________________________________________      ##STR130##                                                                    R.sup.1             R.sup.2      R.sup.3                                       __________________________________________________________________________      ##STR131##                                                                                         ##STR132##  CH.sub.2 Cl                                    ##STR133##                                                                                         ##STR134##  CH.sub.2 Cl                                    ##STR135##         CH.sub.2CH.sub.2OCH.sub.3                                                                   CH.sub.2 Cl                                    ##STR136##         CH.sub.2OCH.sub.3                                                                           CH.sub.2 Cl                                    ##STR137##                                                                                         ##STR138##  CH.sub.2 Cl                                    ##STR139##         CH.sub.2OC.sub.4 H.sub.9 n                                                                  CH.sub.2 Cl                                    ##STR140##                                                                                         ##STR141##  CH.sub.2 Cl                                    ##STR142##         H                                                                                            ##STR143##                                    ##STR144##         H                                                                                            ##STR145##                                    ##STR146##         H            C.sub.2 H.sub.5                                ##STR147##         H            C(CH.sub.3).sub.2C.sub.3 H.sub.7               ##STR148##         H            CH.sub.3                                       ##STR149##         H            CH.sub.3                                       ##STR150##         H                                                                                            ##STR151##                                   __________________________________________________________________________      ##STR152##                                                                     ##STR153##                                                                    X                   X.sub.1      R                                             __________________________________________________________________________     Br                  Br           H and salts                                   J                   J            H and salts                                   Br                  Br                                                                                           ##STR154##                                   __________________________________________________________________________      ##STR155##                                                                     ##STR156##                                                                    R                   R.sup.1      R.sup.2    R.sup.3                            __________________________________________________________________________     Cl                  Cl           Cl         H                                  F                   Cl           Cl         H                                  Cl                  Cl           H          H                                  Cl                  CF.sub.3     H          COOH                               Cl                  Cl           H          COOCH.sub.3                        NO.sub.2            CF.sub.3     H          H                                  H                   CF.sub.3     Cl         H                                  H                   CF.sub.3     Cl         OC.sub. 2 H.sub.5                  Cl                  Cl           H          OCH.sub.3                          __________________________________________________________________________      ##STR157##                                                                    R.sup.1             R.sup.2      R.sup.3    R.sup.4                            __________________________________________________________________________      ##STR158##         H            CH.sub.3   CH.sub.3                            ##STR159##         H            CH.sub.3   CH.sub.3                            ##STR160##         H            CH.sub.3   CH.sub.3                            ##STR161##         H            CH.sub.3   CH.sub.3                            ##STR162##         H            CH.sub.3   CH.sub.3                            ##STR163##         H            CH.sub.3                                                                                   ##STR164##                         ##STR165##         H            CH.sub.3   CH.sub.3                            ##STR166##         H            CH.sub.3   OCH.sub.3                           ##STR167##         H            CH.sub. 3  CH.sub.3                            ##STR168##         H            CH.sub.3   OCH.sub.3                           ##STR169##         H            CH.sub.3   CH.sub.3                            ##STR170##         H            CH.sub.3   CH.sub.3                            ##STR171##         H            CH.sub.3   OCH.sub.3                           ##STR172##         H            CH.sub.3   CH.sub.3                            ##STR173##         H            CH.sub.3   OCH.sub.3                           ##STR174##         H            CH.sub.3   OCH.sub.3                           ##STR175##         H            CH.sub.3   CH.sub.3                            ##STR176##         CH.sub.3     H          CH.sub.3                           __________________________________________________________________________      ##STR177##                                                                     ##STR178##                                                                     ##STR179##                                                                     ##STR180##                                                                    R                   R.sup.1      R.sup.2                                       __________________________________________________________________________     tert. C.sub.4 H.sub.9                                                                              NH.sub.2     SCH.sub.3                                     tert. C.sub.4 H.sub.9                                                                               ##STR181##  SCH.sub.3                                      ##STR182##         NH.sub.2     CH.sub.3                                      __________________________________________________________________________      ##STR183##                                                                    R.sup.1             R.sup.2      R.sup.3                                       __________________________________________________________________________     CH.sub.3            Br           sec. C.sub.4 H.sub.9                          CH.sub.3            Cl           tert. C.sub.4 H.sub.9                         CH.sub.3            Cl                                                                                           ##STR184##                                   CH.sub.2CH.sub.2CH.sub.2                                                                                         ##STR185##                                   __________________________________________________________________________      ##STR186##                                                                    R.sup.1             R.sup.2                                                    __________________________________________________________________________     CH.sub.3            CH.sub.3                                                   CH.sub.3                                                                                            ##STR187##                                                __________________________________________________________________________      ##STR188##                                                                     ##STR189##                                                                    R.sup.1             R.sup.2      R.sup.3                                       __________________________________________________________________________      ##STR190##         sec. C.sub.4 H.sub.9                                                                        H                                              ##STR191##         tert. C.sub.4 H.sub.9                                                                       H                                              ##STR192##         tert. C.sub.4 H.sub.9                                                                       CH.sub.3                                      H                   CH.sub.3     H  salts and esters                           H                   sec. C.sub.4 H.sub.9                                                                        H  salts and esters                           H                   tert. C.sub.4 H.sub.9                                                                       H  salts and esters                           H                   tert. C.sub.4 H.sub.9                                                                       CH.sub.3                                                                          salts and esters                           __________________________________________________________________________      ##STR193##                                                                    R.sup.1                                                                        __________________________________________________________________________      ##STR194##                                                                     ##STR195##                                                                     ##STR196##                                                                    __________________________________________________________________________      ##STR197##                                                                     ##STR198##                                                                    R.sup.1             X                                                          __________________________________________________________________________     H                   CH.sub.3 OSO.sub.3                                         Br                  CH.sub.3 OSO.sub.3                                         CH.sub.3            CH.sub.3 OSO.sub.3                                         CH.sub.3            CF.sub.3 SO.sub.3                                          __________________________________________________________________________      ##STR199##                                                                     ##STR200##                                                                     ##STR201##                                                                     ##STR202##                                                                     ##STR203##                                                                     ##STR204##                                                                     ##STR205##                                                                     ##STR206##                                                                     ##STR207##                                                                     ##STR208##                                                                    R.sup.1             R.sup.2      R.sup.3    R.sup.4                            __________________________________________________________________________     H                   Cl           NH.sub.2   Cl                                 H                   I            I          I                                  Cl                  H            Cl         OCH.sub.3                          Cl                  Cl           H          Cl                                 Cl                  Cl           Cl         OCH.sub.3                          __________________________________________________________________________      ##STR209##                                                                    R.sup.1             R.sup.2      R.sup.3                                       __________________________________________________________________________      ##STR210##         H            H salts, esters, amides                        ##STR211##         CH.sub.3     H salts, esters, amides                        ##STR212##         H            H salts, esters, amides                        ##STR213##         CH.sub.3     H salts, esters, amides                        ##STR214##         H            H salts, esters, amides                        ##STR215##         CH.sub.3     H salts, esters, amides                       __________________________________________________________________________      ##STR216##                                                                     ##STR217##                                                                     ##STR218##                                                                     ##STR219##                                                                     ##STR220##                                                                     ##STR221##                                                                     ##STR222##                                                                     ##STR223##                                                                     ##STR224##                                                                     ##STR225##                                                                     ##STR226##                                                                    R.sup.1                                                                        __________________________________________________________________________     OH                                                                             CH.sub.3                                                                       __________________________________________________________________________      ##STR227##                                                                     ##STR228##                                                                     ##STR229##                                                                     ##STR230##                                                                     ##STR231##                                                                     ##STR232##                                                                    __________________________________________________________________________

It is also possible to apply the compounds of the invention either alone or in combination with other herbicides, in admixture with other crop protection agents, for example agents for combatting pests or phytopathogenic fungi or bacteria. Of further interest is the fact that the compounds of the invention may be mixed with solutions of mineral fertilizers used to eliminate trace element or nutritional deficiencies.

Spreader-stickers and non-phytotoxic oils may be added to the compounds of the invention to ensure that they take effect.

The new compounds have a good fungicidal action for example on phytopathogenic fungi, especially rusts, for instance in cereals and beans. The following fungi for example may be controlled: Puccinia coronata in oats, Puccinia hordei in barley, Puccinia striiformis and Puccinia recondita in wheat, and Uromyces fabae and Uromyces appendiculatus in beans.

Application rates are from 0.2 to 1 kg of active ingredient per hectare.

EXAMPLE 2

Leaves of barley plants of the Asse variety and wheat plants of the Caribo variety, grown in pots, are artificially infected with spores of Puccinia hordei or Puccinia recondita, and the plants are placed for 24 hours in a steam-saturated chamber at 20° to 25° C. The plants are then sprayed with aqueous spray liquors containing (dissolved or emulsified in the water) a mixture of 80% of the active ingredient to be examined and 20% of lignin sulfate, and placed in the greenhouse at from 20° to 22° C. and a relative humidity of from 75 to 80%. The extent to which the rust fungus has spread is assessed after 10 days.

    ______________________________________                                                            Attack after spraying                                                          with liquor containing                                                         0.05% active ingredient                                     Active               Puccinia  Puccinia                                        ingredient           hordei    recondita                                       ______________________________________                                         7                    0         0                                               2                    0         0                                               8                    0         0                                                ##STR233##          1         2                                               prior art (German                                                              Laid-Open Application                                                          DOS 1,567,211)                                                                 Control (untreated)  5                                                         ______________________________________                                          0 = no attack, graduated down to 5 = 100% attack                         

EXAMPLE 3

As described in Example 2, leaves of oat plants of the Flamingskrone variety grown in pots are artificially infected with spores of Puccinia coronata, and sprayed with aqueous suspensions of the active ingredients given in the Table.

    ______________________________________                                                             Attack after spraying                                      Active              with liquor containing                                     ingredient          0.05% active ingredient                                    ______________________________________                                         2                       0                                                      8                       0                                                       ##STR234##             1-2                                                    prior art (German                                                              Laid-Open Application                                                          DOS 1,567,211)                                                                 Control (untreated)     5                                                      ______________________________________                                    

EXAMPLE 4

As described in Example 2, leaves of bean plants of the Mombacher Speck variety grown in pots are artificially infected with spores of Uromyces fabae, and treated with aqueous suspensions of the active ingredients given in the Table.

    ______________________________________                                                             Attack after spraying                                      Active              with liquor containing                                     ingredient          0.05% active ingredient                                    ______________________________________                                         7                       1-2                                                    8                       0                                                       ##STR235##             2                                                      prior art (German                                                              Laid-Open Application                                                          DOS 1,567,211)                                                                 Control (untreated)     5                                                      ______________________________________                                    

Application may be effected for instance in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used; in any case they should ensure a fine distribution of the active ingredient.

For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, etc. and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalene-sulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkylsulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ether, condensation products or sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol esters, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenol polyglycol ethers, alkylaryl polyester alcohols, isotridecyl alcohols, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phospate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably 0.5 to 90%, by weight of active ingredient.

EXAMPLE 5

90 parts by weight of compound 2 is mixed with 10 parts by weight of N-methyl-α-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

EXAMPLE 6

20 parts by weight of compound 8 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 7

20 parts by weight of compound 13 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 8

20 parts by weight of compound 23 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210° and 280° C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 9

20 parts by weight of compound 7 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquid is obtained containing 0.1% by weight of the active ingredient.

EXAMPLE 10

3 parts by weight of compound 46 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

EXAMPLE 11

30 parts by weight of compound 2 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

EXAMPLE 12

40 parts by weight of compound 7 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable aqueous dispersion. Dilution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.04 wt% of active ingredient.

EXAMPLE 13

20 parts of compound 8 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained. 

We claim:
 1. A diurethane of the formula ##STR236##
 2. A diurethane of the formula ##STR237##
 3. A diurethane of the formula ##STR238##
 4. A diurethane of the formula ##STR239##
 5. A diurethane of the formula ##STR240##
 6. A diurethane of the formula ##STR241##
 7. A diurethane of the formula ##STR242##
 8. A diurethane of the formula ##STR243##
 9. A diurethane of the formula ##STR244## 